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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS1989

Role of nitrate and nitrite in the induction of nitrite reductase in leaves of barley seedlings

The role of NO3- and NO2- in the induction of nitrite reductase (NiR) activity in detached leaves of 8-day-old barley (Hordeum vulgare L.) seedlings was investigated. Barley leaves contained 6 to 8 micromoles NO2-/gram fresh weight x hour of endogenous NiR activity when grown in N-free solutions. Supply of both NO2- and NO3- induced the enzyme activity above the endogenous levels (5 and 10 times, respectively at 10 millimolar NO2- and NO3- over a 24 hour period). In NO3(-)-supplied leaves, NiR induction occurred at an ambient NO3- concentration of as low as 0.05 millimolar; however, no NiR induction was found in leaves supplied with NO2- until the ambient NO2- concentration was 0.5 millimolar. Nitrate accumulated in NO2(-)-fed leaves. The amount of NO3- accumulating in NO2(-)-fed leaves induced similar levels of NiR as did equivalent amounts of NO3- accumulating in NO3(-)-fed leaves. Induction of NiR in NO2(-)-fed leaves was not seen until NO3- was detectable (30 nanomoles/gram fresh weight) in the leaves. The internal concentrations of NO3-, irrespective of N source, were highly correlated with the levels of NiR induced. When the reduction of NO3- to NO2- was inhibited by WO4(2-), the induction of NiR was inhibited only partially. The results indicate that in barley leaves in NiR is induced by NO3- directly, i.e. without being reduced to NO2-, and that absorbed NO2- induces the enzyme activity indirectly after being oxidized to NO3- within the leaf.

Non-NASA Center↗
NASA NTRS1988

Cyclic variations in nitrogen uptake rate of soybean plants: effects of external nitrate concentration

Net uptake of NO3- by non-nodulated soybean plants [Glycine max (L.) Merr. cv. Ransom] growing in flowing hydroponic cultures containing 0.5, 1.0 and 10.0 mol m-3 NO3- was measured daily during a 24-d period of vegetative development to determine if amplitude of maximum and minimum rates of net NO3- uptake are responsive to external concentrations of NO3-. Removal of NO3- from the replenished solutions during each 24-h period was determined by ion chromatography. Neither dry matter accumulation nor the periodicity of oscillations in net uptake rate was altered by the external NO3- concentrations. The maxima of the oscillations in net uptake rate, however, increased nearly 3-fold in response to external NO3- concentrations. The maxima and minima, respectively, changed from 4.0 and 0.6 mmol NO3- per gram root dry weight per day at an external solution level of 0.5 mol m-3 NO3- to 15.2 and -2.7 mmol NO3- per gram root dry weight per day at an external solution level of 10.0 mol m-3 NO3-. The negative values for minimum net uptake rate from 10.0 mol m-3 NO3- solutions show that net efflux was occurring and indicate that the magnitude of the efflux component of net uptake was responsive to external concentration of NO3-.

Non-NASA Center↗
DOE OSTI2025

Generation and Study of Am(IV) by Temperature-Controlled Electron Pulse Radiolysis

Used nuclear fuel (UNF) separation techniques that strive to separate radiotoxic americium (Am) from trivalent lanthanide fission products through oxidation state control have increased research efforts surrounding Am(V) and Am(VI). However, equivalent knowledge of the tetravalent state, Am(IV), has remained elusive, particularly in conditions more representative of UNF reprocessing, i.e., in concentrated nitric acid (HNO3). With this in mind, we have used electron pulse radiolysis to study the radiation-induced redox reaction of Am(III) with the oxidizing nitrate radical (NO3?) in 6 M HNO3: Am(III) + NO3? ? Am(IV) + NO3? . These experiments enabled us to observe the growth and decay of Am(IV) in a concentrated acidic solution for the first time. The transient Am(IV) species was found to have a lifetime of ~16 µs?sufficiently long-lived to play a critical mechanistic role in UNF reprocessing systems. Additionally, we performed the first-ever temperature-dependent kinetics study of an actinide element, elucidating unprecedented Arrhenius and Eyring activation parameters for the reaction of Am(III) with NO3?. This new knowledge provides much-needed molecular-level insights into the radiation-induced behavior of Am.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS2003

Uptake of Nitrate and Sulfate on Dust Aerosols during TRACE-P

Aerosol data collected near Asia on the DC-8 aircraft platform during TRACE-P has been examined for evidence of uptake of NO3(-) and SO4(-) on dust surfaces. Data is compared between a sector where dust was predominant and a sector where dust was less of an influence. Coincident with dust were higher mixing ratios of anthropogenic pollutants. HNO3, SO2, and CO were higher in the dust sector than the nondust sector by factors of 2.7, 6.2, and 1.5, respectively. The colocation of dust and pollution sources allowed for the uptake of NO3(-) and nss-SO4(-) on the coarse dust aerosols, increasing the mixing ratios of these particulates by factors of 5.7 and 2.6 on average. There was sufficient nss-SO4(-) to take up all of the NH4(+) present, with enough excess nss-SO4(-) to also react with dust CaCO3. This suggests that the enhanced NO3(-) was not in fine mode NH4NO3. Particulate NO3(-) (p-NO3(-)) constituted 54% of the total NO3(-), (t-NO3(-)) on average, reaching a maximum of 72% in the dust sector. In the nondust sector, p-NO3(-) contributed 37% to t-NO3(-), likely due to the abundance of sea salts there. In two other sectors where the influence of dust and sea salt were minimal, p-NO3(-), accounted for < 15% of t-NO3(-).

Jordan, C. E.↗
NASA NTRS1998

Nitrogen balance for wheat canopies (Triticum aestivum cv. Veery 10) grown under elevated and ambient CO2 concentrations

We examined the hypothesis that elevated CO2 concentration would increase NO3- absorption and assimilation using intact wheat canopies (Triticum aestivum cv. Veery 10). Nitrate consumption, the sum of plant absorption and nitrogen loss, was continuously monitored for 23 d following germination under two CO2 concentrations (360 and 1000 micromol mol-1 CO2) and two root zone NO3- concentrations (100 and 1000 mmol m3 NO3-). The plants were grown at high density (1780 m-2) in a 28 m3 controlled environment chamber using solution culture techniques. Wheat responded to 1000 micromol mol-1 CO2 by increasing carbon allocation to root biomass production. Elevated CO2 also increased root zone NO3- consumption, but most of this increase did not result in higher biomass nitrogen. Rather, nitrogen loss accounted for the greatest part of the difference in NO3- consumption between the elevated and ambient [CO2] treatments. The total amount of NO3(-)-N absorbed by roots or the amount of NO3(-)-N assimilated per unit area did not significantly differ between elevated and ambient [CO2] treatments. Instead, specific leaf organic nitrogen content declined, and NO3- accumulated in canopies growing under 1000 micromol mol-1 CO2. Our results indicated that 1000 micromol mol-1 CO2 diminished NO3- assimilation. If NO3- assimilation were impaired by high [CO2], then this offers an explanation for why organic nitrogen contents are often observed to decline in elevated [CO2] environments.

Non-NASA Center↗
NASA NTRS1991

Expression of characteristics of ammonium nutrition as affected by pH of the root medium

To study the effect of root-zone pH on characteristic responses of NH4+ -fed plants, soybeans (Glycine max inverted question markL. inverted question mark Merr. cv. Ransom) were grown in flowing solution culture for 21 d on four sources of N (1.0 mol m-3 NO3-, 0.67 mol m-3 NO3- plus 0.33 mol m-3 NH4+, 0.33 mol m-3 NO3- plus 0.67 mol m-3 NH4+, and 1.0 mol m-3 NH4+) with nutrient solutions maintained at pH 6.0, 5.5, 5.0, and 4.5. Amino acid concentration increased in plants grown with NH4+ as the sole source of N at all pH levels. Total amino acid concentration in the roots of NH4+ -fed plants was 8 to 10 times higher than in NO3(-)-fed plants, with asparagine accounting for more than 70% of the total in the roots of these plants. The concentration of soluble carbohydrates in the leaves of NH4+ -fed plants was greater than that of NO3(-)-fed plants, but was lower in roots of NH4+ -fed plants, regardless of pH. Starch concentration was only slightly affected by N source or root-zone pH. At all levels of pH tested, organic acid concentration in leaves was much lower when NH4+ was the sole N source than when all or part of the N was supplied as NO3-. Plants grown with mixed NO3- plus NH4+ N sources were generally intermediate between NO3(-)- and NH4+ -fed plants. Thus, changes in tissue composition characteristic of NH4+ nutrition when root-zone pH was maintained at 4.5 and growth was reduced, still occurred when pH was maintained at 5.0 or above, where growth was not affected. The changes were slightly greater at pH 4.5 than at higher pH levels.

NASA Discipline Life Support Systems↗
NASA NTRS1990

Comparative effects of selenite and selenate on nitrate assimilation in barley seedlings

The effect of SeO3= and SeO4= on NO3- assimilation in 8-d-old barley (Hordeum vulgare L.) seedlings was studied over a 24-h period. Selenite at 0.1 mol m-3 in the uptake solutions severely inhibited the induction of NO3- uptake and active nitrate reductases. Selenate, at 1.0 mol m-3 in the nutrient solution, had little effect on induction of activities of these systems until after 12 h; however, when the seedlings were pretreated with 1.0 mol m-3 SeO4= for 24 h, subsequent NO3- uptake from SeO4(=) -free solutions was inhibited about 60%. Sulphate partially alleviated the inhibitory effect of SeO3= when supplied together in the ambient solutions, but had no effect in seedlings pretreated with SeO3=. By contrast, SO4= partially alleviated the inhibitory effect of SeO4= even in seedlings pretreated with SeO4=. Since uptake of NO3- by intact seedlings was also inhibited by SO3=, the percentage of the absorbed NO3- that was reduced was not affected. By contrast, SeO4=, which affected NO3- uptake much less, inhibited the percentage reduced of that absorbed. However, when supplied to detached leaves, both SeO3= and SeO4= inhibited the in vivo reduction of NO3- as well as induction of nitrate reductase and nitrite reductase activities. Selenite was more inhibitory than SeO4= ; approximately a five to 10 times higher concentration of SeO4= than SeO3= was required to achieve similar inhibition. In detached leaves, the inhibitory effect of both SeO3= and SeO4= on in vivo NO3- reduction as well as on the induction of nitrate reductase activity was partially alleviated by SO4=. The inhibitory effects of Se salts on the induction of the nitrite reductase were, however, completely alleviated by SO4=. The results show that in barley seedlings SeO3= is more toxic than SeO4=. The reduction of SeO4= to SeO3= may be a rate limiting step in causing Se toxicity.

NASA Discipline Life Support Systems↗
NASA NTRS1994

Diurnal changes in net uptake rate of nitrate are associated with changes in estimated export of carbohydrates to roots

The rate of NO3- uptake by soybean (Glycine max [L.] Merrill) roots generally declines during the night in association with progressive depletion of the nonstructural carbohydrate pool in the shoot as well as the concentration of carbohydrates in roots. To determine if NO3- uptake rate changes in response to variations in translocation rate of carbohydrates from shoot to roots per se or to carbohydrate status of the roots, the night period was interrupted with a low light level from incandescent lamps to alter the diurnal pattern of NO3- uptake by roots and export of carbohydrate from shoots of nonnodulated soybean. Depletion of NO3- from replenished, complete nutrient solutions containing 1 mM NO3- was measured by ion chromatography and rates of NO3- uptake were calculated. Changes in export of carbohydrates from shoot to roots during intervals of the night period were calculated as the differences between rates of disappearance in contents of nonstructural carbohydrates and their estimated rates of utilization in shoot respiration and growth. A positive, significant correlation occurred between changes in calculated rates of carbohydrate export from shoots and NO3- uptake rates. Conversely, there was no significant correlation between concentrations of nonstructural carbohydrates in roots and NO3- uptake rates. These results support the hypothesis that carbohydrate flux from shoot to roots has a direct role in regulation of nitrogen uptake by the whole plant.

Non-NASA Center↗
NASA NTRS1994

Ammonium and nitrate uptake by soybean during recovery from nitrogen deprivation

Soybean [Glycine max (L.) Merrill] plants that had been subjected to 15 d of nitrogen deprivation were resupplied for 10 d with 1.0 mol m-3 nitrogen provided as NO3-, NH4+, or NH4(+) + NO3- in flowing hydroponic culture. Plants in a fourth hydroponic system received 1.0 mol m-3 NO3- during both stress and resupply periods. Concentrations of soluble carbohydrates and organic acids in roots increased 210 and 370%, respectively, during stress. For the first day of resupply, however, specific uptake rates of nitrogen, determined by ion chromatography as depletion from solution, were lower for stressed than for non-stressed plants by 43% for NO3- resupply, by 32% for NH4(+) + NO3- resupply, and 86% for NH4+ resupply. When specific uptake of nitrogen for stressed plants recovered to rates for non-stressed plants at 6 to 8 d after nitrogen resupply, carbohydrates and organic acids in their roots had declined to concentrations lower than those of non-stressed plants. Recovery of nitrogen uptake capacity of roots thus does not appear to be regulated simply by the content of soluble carbon compounds within roots. Solution concentrations of NH4+ and NO3- were monitored at 62.5 min intervals during the first 3 d of resupply. Intermittent 'hourly' intervals of net influx and net efflux occurred. Rates of uptake during influx intervals were greater for the NH4(+)-resupplied than for the NO3(-)-resupplied plants. For NH4(+)-resupplied plants, however, the hourly intervals of efflux were more numerous than for NO3(-)-resupplied plants. It thus is possible that, instead of repressing NH4+ influx, increased accumulation of amino acids and NH4+ in NH4(+)-resupplied plants inhibited net uptake by stimulation of efflux on NH4+ absorbed in excess of availability of carbon skeletons for assimilation. Entry of NH4+ into root cytoplasm appeared to be less restricted than translocation of amino acids from the cytoplasm into the xylem.

NASA Discipline Number 61-10↗
NASA NTRS1990

Root-zone acidity affects relative uptake of nitrate and ammonium from mixed nitrogen sources

Soybean plants (Glycine max [L.] Merr. cv Ransom) were grown for 21 days on 4 sources of N (1.0 mM NO3-, 0.67 mM NO3- plus 0.33 mM NH4+, 0.33 mM NO3- plus 0.67 mM NH4+, and 1.0 mM NH4+) in hydroponic culture with the acidity of the nutrient solution controlled at pH 6.0, 5.5, 5.0, and 4.5. Dry matter and total N accumulation of the plants was not significantly affected by N-source at any of the pH levels except for decreases in these parameters in plants supplied solely with NH4+ at pH 4.5. Shoot-to-root ratios increased in plants which had an increased proportion [correction of proporiton] of NH4(+)-N in their nutrient solutions at all levels of root-zone pH. Uptake of NO3- and NH4+ was monitored daily by ion chromatography as depletion of these ions from the replenished hydroponic solutions. At all pH levels the proportion of either ion that was absorbed increased as the ratio of that ion increased in the nutrient solution. In plants which were supplied with sources of NO3- plus NH4+, NH4+ was absorbed at a ratio of 2:1 over NO3- at pH 6.0. As the pH of the root-zone declined, however, NH4+ uptake decreased and NO3- uptake increased. Thus, the NH4+ to NO3- uptake ratio declined with decreases in root-zone pH. The data indicate a negative effect of declining root-zone pH on NH4+ uptake and supports a hypothesis that the inhibition of growth of plants dependent on NH4(+)-N at low pH is due to a decline in NH4+ uptake and a consequential limitation of growth by N stress.

NASA Discipline Life Support Systems↗
DOE OSTI2023

2023 American Society for Mass Spectrometry (ASMS) 71st Annual Conference on Mass Spectrometry and Allied Topics

Title (20 words): The investigation of the mechanism for the water splitting by holmium oxide nitrate complex in gas-phase Introduction (120 words): The studies for hydrogen from water splitting is important for clean energy economy as molecular hydrogen is a potential energy carrier. Therefore, understanding the fundamental chemistry of water splitting is essential. The water splitting activated by [Ho(NO3)4]- was previously studied. The suggested mechanism was to first eliminate •NO2 from [Ho(NO3)4]- to make [HoO(NO3)3]-. Then, water was added to form [HoO(NO3)3(H2O)]-, followed by eliminating the •OH to form [HoOH(NO3)3]-. However, we proposed a new mechanism with the formation of [Ho(NO3)3]- prior to the water addition. Once water is added to this intermediate to make [Ho(NO3)3(H2O)]-, the •H is eliminated to form [HoOH(NO3)3]-. Here we have used a labeled experiments with 18-O nitrates. The results to support the new mechanism are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Enhancement of nitrate uptake and growth of barley seedlings by calcium under saline conditions

The effect of Ca2+ on NO3- assimilation in young barley (Hordeum vulgare L. var CM 72) seedlings in the presence and absence of NaCl was studied. Calcium increased the activity of the NO3- transporter under saline conditions, but had little effect under nonsaline conditions. Calcium decreased the induction period for the NO3- transporter under both saline and nonsaline conditions but had little effect on its apparent Km for NO3- both in the presence and absence of NaCl. The enhancement of NO3- transport by Ca2+ under saline conditions was dependent on the presence of Ca2+ in the uptake solution along with the salt, since Ca2+ had no effect when supplied before or after salinity stress. Although Mn2+ and Mg2+ enhanced NO3- uptake under saline conditions, neither was as effective as Ca2+. In longer studies, increasing the Ca2+ concentration in saline nutrient solutions resulted in increases in NO3- assimilation and seedling growth.

NASA Discipline Number 61-10↗
NASA NTRS1992

Comparative kinetics and reciprocal inhibition of nitrate and nitrite uptake in roots of uninduced and induced barley (Hordeum vulgare L.) seedlings

Nitrate and NO2- transport by roots of 8-day-old uninduced and induced intact barley (Hordeum vulgare L. var CM 72) seedlings were compared to kinetic patterns, reciprocal inhibition of the transport systems, and the effect of the inhibitor, p-hydroxymercuribenzoate. Net uptake of NO3- and NO2- was measured by following the depletion of the ions from the uptake solutions. The roots of uninduced seedlings possessed a low concentration, saturable, low Km, possibly a constitutive uptake system, and a linear system for both NO3- and NO2-. The low Km system followed Michaelis-Menten kinetics and approached saturation between 40 and 100 micromolar, whereas the linear system was detected between 100 and 500 micromolar. In roots of induced seedlings, rates for both NO3- and NO2- uptake followed Michaelis-Menten kinetics and approached saturation at about 200 micromolar. In induced roots, two kinetically identifiable transport systems were resolved for each anion. At the lower substrate concentrations, less than 10 micromolar, the apparent low Kms of NO3- and NO2- uptake were 7 and 9 micromolar, respectively, and were similar to those of the low Km system in uninduced roots. At substrate concentrations between 10 and 200 micromolar, the apparent high Km values of NO3- uptake ranged from 34 to 36 micromolar and of NO2- uptake ranged from 41 to 49 micromolar. A linear system was also found in induced seedlings at concentrations above 500 micromolar. Double reciprocal plots indicated that NO3- and NO2- inhibited the uptake of each other competitively in both uninduced and induced seedlings; however, Ki values showed that NO3- was a more effective inhibitor than NO2-. Nitrate and NO2- transport by both the low and high Km systems were greatly inhibited by p-hydroxymercuribenzoate, whereas the linear system was only slightly inhibited.

NASA Program CELSS↗
NASA NTRS1989

Proliferation of maize (Zea mays L.) roots in response to localized supply of nitrate

Maize (Zea mays L.) plants with two primary nodal root axes were grown for 8 d in flowing nutrient culture with each axis independently supplied with NO3-. Dry matter accumulation by roots was similar whether 1.0 mol m-3 NO3- was supplied to one or both axes. When NO3- was supplied to only one axis, however, accumulation of dry matter within the root system was significantly greater in the axis supplied with NO3-. The increased dry matter accumulation by the +N-treated axis was attributable entirely to increased density and growth of lateral branches and not to a difference in growth of the primary axis. Proliferation of lateral branches for the +N axis was associated with the capacity for in situ reduction and utilization of a portion of the absorbed NO3-, especially in the apical region where lateral primordia are initiated. Although reduced nitrogen was translocated to the -N axis, concentrations in the -N axis remained significantly lower than in the +N axis. The concentration of reduced nitrogen, as well as in vitro NO3- reductase activity, was greater in apical than in more basal regions of the +N axis. The enhanced proliferation of lateral branches in the +N axis was accompanied by an increase in total respiration rate of the axis. Part of the increased respiration was attributable to increased mass of roots. The specific respiration rate (micromoles CO2 evolved per hour per gram root dry weight) was also greater for the +N than for the -N axis. If respiration rate is taken as representative of sink demand, stimulation of initiation and growth of laterals by in situ utilization of a localized exogenous supply of NO3- establishes an increased sink demand through enhanced metabolic activity and the increased partitioning of assimilates to the +N axis responds to the difference in sink demand between +N and -N axes.

NASA Discipline Life Support Systems↗
NASA NTRS1989

Efficiency of N use by wheat as a function of influx and efflux of NO sub 3

Since N assimilation is one of the most costly functions of a plant, its efflux before assimilation results in a serious energy cost and loss in efficiency which could decrease yields. Efficient crop production is critical to the Controlled Ecological Life-Support System (CELSS). The objective is to determine the extent of efflux of the N species NO3(-), NH4(+), NO2(-), and urea after uptake, and possible means of regulation. It was found that NO3(-) efflux became serious as its substrate level increased. Efflux/Influx (E/I) of 3NO3(-) was greater in darkness (35 pct) than in light (14 pct) and the ratio greatly increased with increased substrate NO3(-), (up to 45 pct at 10 mM). It seems advantageous to use the lowest possible nutrient concentration of NO3(-). The feasibility of using ClO3(-) as a trapping agent (competitive inhibitor of NO3(-) uptake) for effluxed NO3(-) was assessed and its toxicity determined.

Huffaker, R. C.↗
NASA NTRS1990

Cyclic variations in nitrogen uptake rate in soybean plants: uptake during reproductive growth

Net uptake of NO3- by non-nodulated soybean plants [Glycine max (L.) Merr. cv. Ransom] growing in flowing hydroponic culture was measured daily during a 63 d period of reproductive development between the first florally inductive photoperiod and [unknown word] seed growth. Removal of NO3- from a replenished solution containing 1.0 mol m-3 NO3- was determined by ion chromatography. Uptake of NO3- continued throughout reproductive development. The net uptake rate of NO3- cycled between maxima and minima with a periodicity of oscillation of 3 to 7 d during the floral stage and about 6 d during the fruiting stage. Coupled with increasing concentrations of carbon and C : N ratios in tissues, the oscillations in net uptake rates of NO3- are evidence that the demand for carbohydrate by reproductive organs is contingent on the availability of nitrogen in the shoot pool rather than that the demand for nitrogen follows the flux of carbohydrate into reproductive tissues.

Non-NASA Center↗
DOE OSTI2025

Nitrate-To-Ammonia Electroconversion at Neutral pH on Polycrystalline Vanadium Sulfide Derived from Vanadium Disulfide

The electrochemical nitrate reduction reaction (NO3RR) offers a pathway to produce NH3 for fuel and fertilizer from waste NO3-. In this work, a polycrystalline vanadium sulfide (VSx), which is derived from solvothermally grown and annealed VS2, is shown to exhibit excellent NO3RR activity (2.3 +- 0.6 mg.cm-2 geo..h-1 @ -0.92 VRHE) and Faradaic efficiency to NH4+ (69 +- 6% at -0.69 VRHE) in buffered neutral pH electrolyte containing 0.1 M NO3-. A variety of characterization techniques are leveraged to support the VSx assignment, including X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, selected area electron diffraction, and X-ray diffraction measurements. The VS2 annealing step reduces the oxide character and generates VSx, which, based on the improved NO3RR activity, results in the creation of active sites for NO3- binding. To help shed light on NO3RR on VSx, VS2 is used as a model system, and a grand-canonical density functional theory (GC-DFT) investigation of VS2 shows strong evidence that S vacancies are active sites for NO3RR, where NO3- outcompetes H+ for adsorption at the S-vacancy sites. Moreover, GC-DFT results highlight a thermodynamically favorable reaction to generate NH4+ in an aqueous electrolyte at relevant cathodic potentials. As an annealed material, VSx may contain undersaturated V sites, which show an electronic structure similar to the theoretically calculated S-vacancy site of VS2, and these sites may contribute to the observed increase in NO3RR activity and selectivity for NH4+ on VSx versus unannealed VS2. Finally, kinetic isotope effect measurements suggest that the kinetic rate-limiting step of the NO3RR on VSx is not proton-coupled, indicating it may be the first electron transfer to adsorbed NO3*.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1996

Pressure-Dependent Yields and Product Branching Ratios in the Broadband Photolysis of Chlorine Nitrate

The photolysis of chlorine nitrate was studied using broadband flash photolysis coupled with long-path ultraviolet-visible absorption spectroscopy. Branching ratios for the Cl + NO3 and ClO + NO2 product channels were determined from time-dependent measurements of ClO and NO3 concentrations. Yields of the ClO and NO3 products displayed a dependence on the bath gas density and the spectral distribution of the photolysis pulse. Product yields decreased with increasing bath gas density regardless of the spectral distribution of the photolysis pulse; however, the decrease in product yield was much more pronounced when photolysis was limited to longer wavelengths. For photolysis in a quartz cell (lambda > 200 nm) the yield decreased by a factor of 2 over the pressure 10-100 Torr. In a Pyrex cell (lambda > 300 nm), the yield decreased by a factor of 50 over the same pressure range. When photolysis was limited to lambda > 350 nm, the yield decreased by a factor of 250. Branching ratios for the photolysis channels [ClONO2 + h.nu yields ClO + NO2 (1a) and ClONO2 + h.nu yields Cl + NO3 (lb)] were determined from the relative ClO and NO3 product yields at various pressures. Although the absolute product yield displayed a pressure dependence, the branching between the two channels was independent of pressure. The relative branching ratios (assuming negligible contributions from other channels) are 0.61 +/- 0.20 for channel 1a and 0.39 +/- 0.20 for channel lb for photolysis with lambda > 200 nm and 0.44 +/- 0.08 for channel 1a and 0.56 +/- 0.08 for channel 1b for photolysis with lambda > 300 nm. The implications of these results for the chemistry of the lower stratosphere are discussed.

Nickolaisen, Scott L.↗